EP0882013B1 - Preparation of diamine carbamates - Google Patents

Preparation of diamine carbamates Download PDF

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Publication number
EP0882013B1
EP0882013B1 EP97905758A EP97905758A EP0882013B1 EP 0882013 B1 EP0882013 B1 EP 0882013B1 EP 97905758 A EP97905758 A EP 97905758A EP 97905758 A EP97905758 A EP 97905758A EP 0882013 B1 EP0882013 B1 EP 0882013B1
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EP
European Patent Office
Prior art keywords
diamine
carbon dioxide
amine
preparation
hexamethylene diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP97905758A
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German (de)
French (fr)
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EP0882013A1 (en
Inventor
John Harry Orth
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups

Definitions

  • This invention relates to an improved process for the preparation of diamine carbamates by contacting a liquid diamine with carbon dioxide gas.
  • Polyamine carbamates have been produced in the past by adsorbing the polyamine on a particulate carrier and then reacting the polyamine with carbon dioxide. See Brodoway U.S. Patent 4,102,801.
  • Another route to carbamate salts is to react an amine in solution with gaseous or dissolved carbon dioxide.
  • Hexamethylene diamine carbamate has been prepared by the known process of reacting hexamethylene diamine and carbon dioxide in chlorobenzene solvent.
  • Polyamine carbamates are useful as curing agents for elastomers.
  • the primary diamine carbonates prepared by the process described herein are useful as intermediates for the preparation of polyamides.
  • This invention provides a process for the preparation of primary diamine carbamates which comprises reacting a liquid spray of primary diamine with gaseous carbon dioxide, in the optional presence of an inert propellant.
  • the process of the present invention concerns the preparation of primary diamine carbamates by the spraying of a liquid primary diamine into carbon dioxide gas, optionally in the presence of an inert propellant.
  • the diamine must be utilized above its melting point, i.e., in the liquid state. If the melting point of the diamine starting material lies above room temperature, or above whatever other temperature is chosen to be the temperature of the reaction, the diamine must first be heated above its melting temperature to allow for spraying.
  • the liquid diamine is propelled by pressure into the gaseous carbon dioxide, optionally using an inert gas, for example, but not limited to, nitrogen as a propellant.
  • an inert gas for example, but not limited to, nitrogen as a propellant.
  • Suitable diamines include primary aliphatic, cycloaliphatic, and aromatic diamines having 2-14 carbon atoms.
  • the most preferred diamine is hexamethylene diamine.
  • the melting point of industrially prepared, commercially available hexamethylene diamine is 39-40°C, and thus, the hexamethylene diamine must be heated above this temperature prior to reaction.
  • the process of the present invention avoids the problems of solvent handling prior to and during reaction and the effort associated with solvent removal from the diamine carbamate product that is required by some available processes and avoids the need for cryogenic grinding as required in other processes.
  • Spraying the molten amine into the carbon dioxide causes it to react vigorously, promptly, and completely.
  • the diamine, the carbon dioxide or both may be mixed with an inert gas propellant to insure prompt and intimate contact between the diamine and the carbon dioxide.
  • the spraying of the molten diamine in small droplets insures maximum contact surface and for the rapid reaction of diamine with the carbon dioxide.
  • the optimum droplet size will vary. Optimum particle size for each diamine may be readily determined. Under optimum droplet size conditions, the reaction will be complete in a short time, essentially instantaneously.
  • carbon dioxide it is, of course, necessary for the carbon dioxide to be present in the reaction zone in an amount at least stoichiometrically equal to the amount of diamine in order to achieve complete reaction. Usually carbon dioxide is present in the reaction mass in excess of the stoichiometric amount.
  • Carbon dioxide may be used at room temperature and may be used with an inert propellant such as nitrogen gas.
  • Representative amines that may be employed in the process of this invention include: 1,3-diaminopropane, 1,6-diaminohexane (hexamethylene diamine), 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,10-diaminodecane, 1, 12-diaminododecane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,4-phenylenediamine, and 1,3-phenylenediamine.
  • 1,3-diaminopropane 1,6-diaminohexane (hexamethylene diamine), 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,10-diaminodecane, 1, 12-diaminododecane, 1,4-
  • Preferred diamines are 1,6-diaminohexane (hexamethylene diamine), 1,12-diaminododecane and 4,4'-methylenebis-(cyclohexylamine). Most preferred is 1,6-diaminohexane (hexamethylene diamine).
  • Hexamethylene diamine, 98.5% pure, 35 g was charged to a 125 mL nitrogen pressurized atomizer.
  • the hexamethylene diamine in the atomizer was heated by means of a hot water bath on a stirrer/hot plate to approximately 35°C.
  • the outlet of the atomizer was directed toward the opening of a rectangular receiver constructed of corrugated paper board coated with a Teflon® fluoropolymer film.
  • a stream of carbon dioxide gas from a laboratory sized cylinder was directed through a dispersing funnel at the rear of the hexamethylene diamine charged atomizer so as to encompass the hexamethylene diamine spray in a concurrent flow of carbon dioxide.
  • the atomizer spray tip was indirectly heated with an infrared heat lamp to avoid a build up of hexamethylene diamine carbamate product.
  • the carbon dioxide flow was started followed by startup of the hexamethylene diamine spray.
  • the finely divided hexamethylene diamine droplets were instantly converted to a fine white powder that melting point determination (m.p. 150-160°C) proved to be predominantly hexamethylene diamine carbamate.

Description

  • This invention relates to an improved process for the preparation of diamine carbamates by contacting a liquid diamine with carbon dioxide gas.
    • TECHNICAL BACKGROUND
  • Polyamine carbamates have been produced in the past by adsorbing the polyamine on a particulate carrier and then reacting the polyamine with carbon dioxide. See Brodoway U.S. Patent 4,102,801.
  • Another route to carbamate salts is to react an amine in solution with gaseous or dissolved carbon dioxide.
  • Hexamethylene diamine carbamate has been prepared by the known process of reacting hexamethylene diamine and carbon dioxide in chlorobenzene solvent.
  • Leon Segal in Applied Spectroscopy Vol. 17, No. 1, 1963 at pages 21-22, discloses the reaction of hexamethylene diamine in the solid state with atmospheric carbon dioxide.
  • Polyamine carbamates are useful as curing agents for elastomers. The primary diamine carbonates prepared by the process described herein are useful as intermediates for the preparation of polyamides.
    • SUMMARY OF THE INVENTION
  • This invention provides a process for the preparation of primary diamine carbamates which comprises reacting a liquid spray of primary diamine with gaseous carbon dioxide, in the optional presence of an inert propellant.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The process of the present invention concerns the preparation of primary diamine carbamates by the spraying of a liquid primary diamine into carbon dioxide gas, optionally in the presence of an inert propellant. The diamine must be utilized above its melting point, i.e., in the liquid state. If the melting point of the diamine starting material lies above room temperature, or above whatever other temperature is chosen to be the temperature of the reaction, the diamine must first be heated above its melting temperature to allow for spraying.
  • The liquid diamine is propelled by pressure into the gaseous carbon dioxide, optionally using an inert gas, for example, but not limited to, nitrogen as a propellant.
  • Suitable diamines include primary aliphatic, cycloaliphatic, and aromatic diamines having 2-14 carbon atoms. The most preferred diamine is hexamethylene diamine. The melting point of industrially prepared, commercially available hexamethylene diamine is 39-40°C, and thus, the hexamethylene diamine must be heated above this temperature prior to reaction.
  • The process of the present invention avoids the problems of solvent handling prior to and during reaction and the effort associated with solvent removal from the diamine carbamate product that is required by some available processes and avoids the need for cryogenic grinding as required in other processes.
  • The process of the invention for primary aliphatic diamines may be summarized by the following equation for linear aliphatic primary diamines where x is a number from 2-14: H2N(CH2)xNH2 (liquid) + CO2 (gas) → +H3N(CH2)xNHCOO- (solid)
  • Spraying the molten amine into the carbon dioxide causes it to react vigorously, promptly, and completely. The diamine, the carbon dioxide or both may be mixed with an inert gas propellant to insure prompt and intimate contact between the diamine and the carbon dioxide. The spraying of the molten diamine in small droplets insures maximum contact surface and for the rapid reaction of diamine with the carbon dioxide.
  • In general, the smaller the droplet size, the easier it is to complete reaction. For each diamine employed, the optimum droplet size will vary. Optimum particle size for each diamine may be readily determined. Under optimum droplet size conditions, the reaction will be complete in a short time, essentially instantaneously.
  • It is, of course, necessary for the carbon dioxide to be present in the reaction zone in an amount at least stoichiometrically equal to the amount of diamine in order to achieve complete reaction. Usually carbon dioxide is present in the reaction mass in excess of the stoichiometric amount.
  • Carbon dioxide may be used at room temperature and may be used with an inert propellant such as nitrogen gas.
  • Representative amines that may be employed in the process of this invention include: 1,3-diaminopropane, 1,6-diaminohexane (hexamethylene diamine), 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,10-diaminodecane, 1, 12-diaminododecane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,4-phenylenediamine, and 1,3-phenylenediamine. Preferred diamines are 1,6-diaminohexane (hexamethylene diamine), 1,12-diaminododecane and 4,4'-methylenebis-(cyclohexylamine). Most preferred is 1,6-diaminohexane (hexamethylene diamine).
  • In the following example all parts and percentages are in parts by weight unless otherwise specified.
    • EXAMPLE 1 Preparation of hexamethylene diamine carbamate
  • Hexamethylene diamine, 98.5% pure, 35 g, was charged to a 125 mL nitrogen pressurized atomizer. The hexamethylene diamine in the atomizer was heated by means of a hot water bath on a stirrer/hot plate to approximately 35°C. The outlet of the atomizer was directed toward the opening of a rectangular receiver constructed of corrugated paper board coated with a Teflon® fluoropolymer film. A stream of carbon dioxide gas from a laboratory sized cylinder was directed through a dispersing funnel at the rear of the hexamethylene diamine charged atomizer so as to encompass the hexamethylene diamine spray in a concurrent flow of carbon dioxide. The atomizer spray tip was indirectly heated with an infrared heat lamp to avoid a build up of hexamethylene diamine carbamate product. The carbon dioxide flow was started followed by startup of the hexamethylene diamine spray. The finely divided hexamethylene diamine droplets were instantly converted to a fine white powder that melting point determination (m.p. 150-160°C) proved to be predominantly hexamethylene diamine carbamate.

Claims (8)

  1. A process for the preparation of primary diamine carbamates which comprises reacting a liquid spray of primary diamine with gaseous carbon dioxide, in the optional presence of an inert propellant.
  2. The process of Claim 1 in which the diamine is selected from the group consisting of aliphatic and cycloaliphatic diamines having 2-14 carbon atoms.
  3. The process of Claim 1 wherein the amine is selected from the group consisting of 1,2-diaminopropane, 1,6-diaminohexane, 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,10-diaminodecane, 1,12-diaminododecane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,4-phenylenediamine, and 1,3-phenylenediamine.
  4. The process of Claim 3 in which the amine is hexamethylene diamine [1,6-diamino hexane].
  5. The process of Claim 3 in which the amine is 1,12-diaminododecane.
  6. The process of Claim 3 in which the amine is 4,4'-methylenebis(cyclohexylamine)
  7. The process in Claim 1 conducted in the presence of an inert propellant.
  8. The process of Claim 7 wherein the propellant is nitrogen gas.
EP97905758A 1996-02-06 1997-02-04 Preparation of diamine carbamates Expired - Lifetime EP0882013B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1124696P 1996-02-06 1996-02-06
US11246P 1996-02-06
PCT/US1997/001800 WO1997029083A1 (en) 1996-02-06 1997-02-04 Preparation of diamine carbamates

Publications (2)

Publication Number Publication Date
EP0882013A1 EP0882013A1 (en) 1998-12-09
EP0882013B1 true EP0882013B1 (en) 2001-09-05

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EP97905758A Expired - Lifetime EP0882013B1 (en) 1996-02-06 1997-02-04 Preparation of diamine carbamates

Country Status (5)

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US (1) US5981797A (en)
EP (1) EP0882013B1 (en)
JP (1) JP2000504688A (en)
DE (1) DE69706524T2 (en)
WO (1) WO1997029083A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20041229A1 (en) * 2004-06-18 2004-09-18 Milano Politecnico PROCEDURE FOR THE PREPARATION OF PRIMARY AND SECONDARY POLYAMINE CARBAMATES
DE102007022445A1 (en) * 2007-05-10 2008-11-13 Evonik Degussa Gmbh Process for the preparation of amines
US9126903B2 (en) 2011-02-14 2015-09-08 Sogang University Research Foundation Preparation method for solid powder of a carbamic acid derivative
KR101305053B1 (en) * 2011-02-14 2013-09-11 서강대학교산학협력단 Method for Producing Carbamic Acid Derivative Powder
CN104592058A (en) * 2015-02-18 2015-05-06 中国科学院长春应用化学研究所 Preparation method for organic amine carbaminate
EP3274075A4 (en) 2015-03-23 2018-11-21 BASF Corporation Carbon dioxide sorbents for indoor air quality control
KR101741899B1 (en) 2015-06-04 2017-06-15 한국과학기술원 Deep Eutectic Solvent for absorbing carbon dioxide, Method for manufacturing the same and Carbon dioxide absorbent comprising the same
EP3414004A4 (en) 2016-02-12 2019-10-09 BASF Corporation Carbon dioxide sorbents for air quality control
JP2019151630A (en) * 2018-03-02 2019-09-12 学校法人早稲田大学 Polyfunctional compound and method for producing the same, amic acid compound and method for producing the same, and method for producing imide compound
CN114163355B (en) * 2021-11-04 2022-11-18 浙江大学 Method for improving reaction conversion rate of amine and carbon dioxide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102801A (en) * 1977-03-24 1978-07-25 E. I. Du Pont De Nemours And Company Process for making polyamine carbamates

Also Published As

Publication number Publication date
US5981797A (en) 1999-11-09
WO1997029083A1 (en) 1997-08-14
DE69706524T2 (en) 2002-07-11
EP0882013A1 (en) 1998-12-09
DE69706524D1 (en) 2001-10-11
JP2000504688A (en) 2000-04-18

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